CN1207146A - Controlled hysteresis nonwoven laminates - Google Patents

Abstract

There is provided herein a multilayer material comprising of layers of elastomeric films, fiber, or webs wherein at least one layer is comprised of an elastomeric polyolefin and at least one additional layer is comprised of an elastomer selected from the group consisting of polyurethanes, copolyether esters, polyamide polyether block copolymers, ethylene vinyl acetates (EVA), and block copolymers having the general formula A-B-A', A-B-A-B or A-B like copoly(styrene/ethylene-butylene), (polystyrene/poly(ethylene-butylene)/polystyrene), and poly(styrene/ethylene-butylene/styrene). Such a material also includes at least one gatherable web to which the elastic webs are joined and may be made into a personal care product, an infection control product, a protective cover or a garment.

Description

The composite elastic material of controlled hysteresis and personal care product

Background of invention

Form fiber with the thermoplastic resin that squeezes out, film and fiber web have the several years, are polyolefin for the prevailing thermoplastic of this application, especially polypropylene, but the desirable characteristic of the relative final products of each material respectively has its distinctive merits and demerits.

Bondedfibre fabric is the typical products that can be made by such polymer, and it can be used for range of application widely, and for example the personal care product resembles diaper, and feminine hygiene article and incontinence product infect control goods, coat and other goods.The bondedfibre fabric that is used in these purposes usually is the form of lamination, and it has several layers of melt-blown nonwoven fabric and spunbond bondedfibre fabric, as spunbond/meltblown/spunbonded (SMS) lamination, the SMMS lamination and even lamination have 6 layers or more multi-layered.

Be used to make fiber, film and fibroreticulate a kind of special desirable thermoplastic polymer are flexible.An example that is used to produce these product combination things has been disclosed in the US 4 that authorizes people such as Wisneski, 663, in 220, wherein fiber is by a kind of polymer production of A-B-A ' block copolymer, and " A " and " A ' " respectively is a kind of thermoplasticity end-block that comprises the styrene part, " B " handles auxiliary agent for block and polyolefin in the elasticity poly-(ethene-butylene).

Though so far polyolefin such as polyethylene and polypropylene are stiff, in polymer and catalyst technology, newly develop a kind of material that is referred to as metallocene polymers.The polymer of producing by the metallocene method has some characteristics that are different from the polymer of producing by traditional Z-N and other system, and some polymer of described polymer can be flexible.Metallocene based on elastic polyolefin has stretching and the retraction characteristic that is different from the known elasticity body.

The inventor has had now found that a kind of multi-layer laminate, the some of them layer is made by elastic polyolefin, this elastic polyolefin is handled by metallocene and is produced, some layers are to make by traditional elastomer, make it allow the stretching of final products and retraction characteristic satisfy very high degree requirement.It is believed that only mixing different elastomers before fiber product is a kind of good method, its former because: first, mixture, similar chemical reaction, be unpredictable, and in fact the result is the desirable characteristic that has increased fabric, second, some polymer is immiscible, or can not make a kind of mixture.

An object of the present invention is to provide laminated product, so that the control that the properties of materials of being produced by such laminated product can be good with at least one elastic polyolefin layer and at least one other elastomeric polymer layer.Summary of the invention

Multi-layer laminate provided by the invention is by several layers of elastic film fiber or fiber web and constitute, wherein one deck is made up of elastic polyolefin at least, and at least one extra play is to be selected from the elastomer that comprises kind what follows to form: polyurethanes, copolyether ester, polyamide polyether block copolymer, ethylene vinyl acetate (EVA), with general formula be the block copolymer of A-B-A ' or A-B, for example resemble copolymerization (styrene/ethylene-butylene), (polystyrene/poly-(ethene-butylene)/polystyrene and poly-(styrene/ethylene-butylene/styrene).Such laminated product can be made into personal care product, and control infects goods, cover layer or coat.Definition

Employed in this application term " fabric " or fiber web " be meant the fiber web of structure with each fiber that a kind of quilt places mutually or line, but be not a kind of mode such as a kind of knit goods that can be easy to identify.Bondedfibre fabric or fiber web are formed by many processes, for example, and melt-blown process method, spunbond process and bonded carded fibrous web process.The basic weight of bondedfibre fabric is often expressed as ounce per square yard (osy), or gram/square metre (gsm), and fibre diameter generally is expressed as micron, (annotate osy be converted into gsm 33.91 multiply by osy).Be meant that at this employed term " microfiber " having average diameter is not more than 75 microns small diameter fibers, for example average diameter is 0.5 micron to 50 microns, and especially microfiber can have 2 microns to 40 microns average diameter.Be used to represent that another conventional unit of fibre diameter is a DENIER, it is defined as the per 9000 meters long gram number of fiber.For example, can be at the diameter of a kind of polypropylene fibre of given micron expression by taking advantage of the result of its square to convert DENIER to 0.00629, like this, 15 microns polypropylene fibre is about 1.42 DENIER (15 ²* 0.00629=1.415).

Term " spun-bonded fibre " expression is than the fiber of minor diameter as used herein, it be by molten thermoplastic material with many tiny from a spinning plate of the form of long filament, normally extrude and make the diameter of the long filament of extruding to reduce rapidly to form in the circular capillaries, this mode, for example revealed in following patent, people's such as Appel US 4,340,563, people's such as Dorschner 3,692,618, people's such as Matsuki US 3,802,817, the US 3,338 of Kinney, 992 and US 3,341,394, the US 3 of Hartman, 502,763 and people's such as Dobo US3,542,615.Spun-bonded fibre is not normally piled up when it is placed into the collection surface.Spun-bonded fibre generally is continuous and average diameter is greater than 7 microns, especially between 10 to 20 microns.

Term " meltblown fibers " is meant the fiber that is formed by following manner as used herein, molten thermoplastic is pressed through that some are thin, is generally circular mold pressing pores and becomes fusion yarn or long filament and enter into in the high velocity air (as air) of convergence, this air-flow attenuates reducing its diameter the long filament of molten thermoplastic, and makes it reach the microfiber diameter.Subsequently, meltblown fibers is transmitted by high velocity air and is placed on and collects the surface upward to form a kind of fiber web of meltblown fibers Random assignment.This process is revealed, and for example US 3,849, and 241.Meltblown fibers is a microfiber, and it is continuous or discrete, and average diameter is generally less than 10 microns, and when being placed into the collection surface, normally pile up.

Term " polymer " as used herein " generally include following material, but be not restricted to this, homopolymers, copolymer, for example block, grafting, random and alternation copolymer, terpolymer etc. and its mixture and variant.In addition, unless there is other explanation to limit term " polymer " " will comprise all possible geometrical configuration of material.These configurations comprise isotaxy, syndiotaxy and atactic symmetries, but and be limited to this.

Term " machine direction " or the MD meaning is the fabric length direction that fabric makes progress at its producer as used herein.The term " cross-machine " or the CD meaning are the width of fabric directions, promptly common direction perpendicular to MD.

The fiber that one or more extruding of a kind of polymer form is only used in term " one pack system " fibring as used herein.This does not mean that formed fiber from for painted, and antistatic behaviour is lubricated, gets rid of in a kind of polymer of a small amount of additive that hydrophily etc. are added.These additives for example are used for painted titanium dioxide, generally are to be less than 5% (weight), and generally more than 2% (weight).

Term " conjugate fibre " expression is to be extruded from the extruder that separates by at least two kinds of polymer but spinned together to form a fiber that fiber is made as used herein.Conjugate fibre is also represented multicomponent or bicomponent fiber sometimes.These polymer generally are distinguishing mutually, although conjugate fibre can be a multicomponent fibre.Arrange in described polymer obvious zone with constant substantially layout on the cross section of conjugate fibre, and be that length direction along conjugate fibre extends continuously.The configuration of for example so a kind of conjugate fibre can be that skin/core pattern is arranged, and wherein a kind of polymer is centered on by another kind of polymer, perhaps can be to arrange side by side, perhaps can be that " island " (it is starlike) type is arranged.Some conjugate fibres are at people's such as Kaneko US 5,108,820, and people's such as Strack US 5,336,552 reports among people's such as Pike the US 5,382,400.For two kinds of component fibers, the ratio of its polymer is 75/25,50/50,25/75, perhaps any other desirable ratio.

Term " two compositions (compound) fiber " expression is by at least two kinds of polymer as used herein, with a kind of form of mixture, extrudes and the fiber that forms from identical extruder.Term " mixture " is defined in the back.Biconstitutent fibre does not have the obviously arrangement in zone of the constant relatively layout of its each polymers compositions on the transverse cross-sectional area of fiber, and each polymer is discontinuous along the whole length of fiber, and common formed fiber or fibrillation are at random from start to finish.Biconstitutent fibre is also represented multi-constituent fibre sometimes.General typical this fibrid is revealed, for example, and the US 5,108,827 of Gessner.Conjugation and biconstitutent fibre also are disclosed in the textbook polymeric blends and combination of John A.Manson and Leslie H.Sperling, Plenum Press1976 version, New York, the part 273-277 page or leaf of IBSN 0-306-30831-2 Plenum PublishingCorporation.

Term " mixture " means two or more mixture of polymers as used herein, and term " alloy (alloy) " means a subclass of mixture, and wherein component is immiscible, but has passed through compatible processing." compatibility " and " unmixability " be defined as mixture have respectively negative value and on the occasion of the free energy of mixing.In addition, " compatible processing " be defined as in order to make the technical process of the interface modification that a kind of alloy carries out the immiscible polymer mixture.

As used herein term " pressure roller " be illustrated on the fiber web and under device or some rollers, it is used for compressing the fiber web as with the pre-bonding or just bonding spun-bonded fibre net form of just having made, so that for further processing technology gives it with enough integralities, but with respect to other adhesion technique such as TAB heat bonding, waterpower winding and ultrasonic wave are bonding not to be strong bonding.Pressure roller is the extrusion fiber net slightly, so that increase its self-adhesion and its integrality.It is very suitable that pressure roller is finished this function, but it also has some shortcomings.One of shortcoming be pressure roller in fact compacting fiber web, thereby cause that the bulk density of fabric or bulkiness reduce, this is undesirable for instructions for use.Second and be that even more serious shortcoming is that fabric is wrapped on one or two rollers sometimes, thus for cleaning roller causes the fabric production line stop, productivity ratio obviously reduces between down period.The 3rd shortcoming of pressure roller is if produce small defective in fiber web is shaped, for example a dropping of polymer is formed on the fiber web, pressure roller can force dropping to enter on the porose conveyer belt, and most of fiber is to be formed on its conveyer belt, can cause the imperfection of conveyer belt like this and will damage this conveyer belt.

The meaning of term " hot-air scraper " or HAK is the technology of the fiber just made of a kind of preliminary treatment or initial processing as used herein, so that for further processing technology is given its enough integrality, but with respect to other adhesion technique such as heat bonding, waterpower winding and ultrasonic wave are bonding, and it is not strong bonding.The hot-air scraper is a kind of device, this device focuses on the air flow of a heating, its air flow has very high flow velocity, and flow velocity is generally 1000～10000 feet per minutes (fpm) (305～3050 meters/minute), this air flow directive nonwoven web at once after fiber web is shaped.For the ordinary hot thermoplastic polymer that is used for spun-bond process, air themperature is generally 200 to 500 °F (93 to 290 ℃).By at least one width is 1/8 to 1 inch (3 to 25mm), especially the slit of 3/8 inch (9.4mm) air flow putting in order and guide HAK to focus on, its slit is that conduct is towards the fibroreticulate outlet that adds hot-air, and slit is on fibroreticulate whole width, arranges for cross-machine direction substantially.In other embodiments, some slits close mutually or separate arrangement with minim gap also can be arranged.At least one slit is preferably, but unnecessary be continuous, for example it can have closely spaced hole by some and forms.HAK has the space of a sealing, is adding before hot-air draws from slit being used for, and configuration and storage dress add hot-air.The enclosure space pressure of HAK is preferably 1.0 to 12.0 inchess of water(in H (2 to 22mmHg), and HAK is positioned on the shaping wire rod 0.25 to 10 inch, is preferably 0.75 to 3.0 inch (19 to 76mm).In a specific embodiments, the cross-sectional area (being the enclosure space cross-sectional area on the machine direction) of the enclosure space of the HAK that flows for horizontal direction is the twice of whole slit discharge area at least.Because the porose wire rod that spunbond polymer forms thereon generally is to move with two-forty, fibroreticulate any special part was subjected to the time of the air effect of being discharged by the hot-air scraper less than 1/10th seconds, compared its time and was generally centisecond with the air adhesion technique that penetrates with very long time of staying.The HAK technical process has the large-scale changeability and the controllability of air themperature, air velocity and the fibroreticulate distance of HAK enclosure space distance at least.

Penetrate air bonding or " TAB " as used herein, represent a kind of process of bonding nonwoven conjugate fibre, wherein be enough to be heated to fibroreticulate one of them the air of polymer fiber fusion that makes its manufacturing and be forced to and pass through fiber web.Air velocity is 100 to 500 feet of per minutes, and the time of staying can only be 6 seconds.It is bonding that the fusion of polymer and solidifying has again constituted.Penetrate the bonding second step adhesion process that is considered to usually of air.It is bonding to require at least a component melts to finish by TAB, and this just limits fiber web has two kinds of components such as conjugate fibre or it at least and comprise a kind of adhesive.

Term " loop bonding " expression is for example according to people's such as Strack US 4,891,957 or Carey as used herein, and the US 4,631,933 of Jr is a kind of stitching of material.

" ultrasonic bonds " means fabric is passed through a kind of technical process of being finished between sound collector and anvil roller as used herein, as the explanation in the US 4,374,888 of Bornslaeger.

" focus bonding " relates to fabric or with the fiber web of bonded fiber as used herein, passes through between the calender of heating and anvil roller.Calender is shaped on decorative pattern usually in some way, but may not be always, so that whole fabric can be not bonded across the whole surface of its calender, and anvil roller is normally smooth.Therefore, the reason that has an aesthetic owing to function has been developed the various patterns of calender.A kind of example of pattern is to have some points, and is HansenPennings or " H﹠amp; P " pattern, it has 30% adhesion area and 200 bounding point/square inches, as being reported in the US 3,855,046 of Hansen and Pennings.H﹠amp; The P pattern side's of having point or pin adhesion area, 0.038 inch of each pin lateral dimensions (0.965mm) wherein, 0.070 inch of the spacing between the pin (1.778mm), 0.023 inch of the bonding degree of depth (0.584mm).Resulting pattern has 29.5% adhesion area.Another typical some bonding patterns decorative pattern is Hansen Pennings or " EHP " bonding patterns decorative pattern of expansion, its generation has 15% adhesion area, policy has 0.037 inch of lateral dimensions (0.94mm), 0.097 inch of needle gage (2.464mm), 0.039 inch of the bonding degree of depth (0.991mm).Another some bonding patterns decorative pattern that typically is designed to " 714 " has the policy adhesion area, and wherein every needle set has 0.023 inch of lateral dimensions, 0.062 inch of the spacing between pin (1.575mm), 0.033 inch of the bonding degree of depth (0.838mm).The pattern that is obtained has about 15% adhesion area.And another general pattern decorative pattern is the C-Star pattern, and it has 16.9% adhesion area." corduroy " pattern that the C-Star pattern has travers or disconnected by outstanding star.Some other common pattern comprise have a repetition and do not overlap the square pattern of square a little, the pattern that it has 16% adhesion area and a kind of wire rod to knit approximately, association resembles a kind of window net as title, it has 19% adhesion area approximately.Generally, adhesion area percentage is that 10% to 30% of the fibroreticulate area of fabric stratiform does not wait.As known in the art, spot bonding is fixed together each layer, and by binder filaments and/or fiber in every layer integrality is given to each layer.

The art of speaking as used herein " bonding window " is meant and is used for bondedfibre fabric is bonded together, and completes successfully the temperature range of this bonding calender.For spunbond polypropylene, bonding window is generally 270 °F to 310 °F (132 ℃ to 154 ℃).If be lower than 270 °F, polypropylene can not be enough to be melted with bonding, is higher than 310 °F, and polypropylene also can be attached to excessive fusion on the calender.Polyethylene has narrower bonding window.

Term " retraction " as used herein, expression is when by the applying of biasing force, and its material stretches thereupon, during the biasing force end, the contraction of the material that is stretched.For example, be that 1 inch material extends 50% by being stretched to 1.5 inches if having loose unbiased length, material will have a tensile elongation so, and this tensile elongation is 150% of its loose length.After bias voltage and tensile force were removed, if the material that this sample is stretched shrinks, it retracts to length was 11 inches, so material 80% (0.4 inch) of its elongation that will bounce back.

Term " constriction " or tradable " neck is to stretching " represent a kind of method of prolongation bondedfibre fabric on machine direction usually as used herein, reach desirable quantitative value thereby reduce its width in the mode of controlling.Controlled stretch can occur in cooling, under room temperature or the higher temperature, and is an increment that is limited in the whole dimension on the inherent draw direction of the extended range that requires the fracture fabric, as a rule, is about 1.2 to 1.4 times.When loose, fiber web shrinks towards its life size.For example, this process is disclosed in the US4 of Meitner and Notheis, 443,513 and the US 4,965,122 of Morman, US 4,981,747 and US 5,114,781 in.

Term " flexible " and " elastomeric " are stretchable for a kind of material that fiber, film or fabric are meant when applying a biasing force as used herein, making the biasing force length that is stretched is 150% or 1.5 times of its loose unstretched length, and when the stretching biasing force is removed, its 50% of prolongation at least that will bounce back.

A kind of elastomeric material represented in term " composite elastic material " as used herein, and it can be a kind of multi-component material or multilayer material.For example, a kind of multilayer material can have at least one elastic layer, and this elastic layer is connected at least one shrinkable layers at the two positions place at least, so that shrinkable layers is retracted between the position that connects elastic layer.A kind of like this composite elastic material can stretch and reach such degree, so that the non-elastomeric material of shrinking between bond locations prolongs elastomeric material.For example, one type MULTILAYER COMPOSITE elastomeric material is by 4,720,415 announcements of US of people such as Vander Wielen, and its full content can draw and is reference, wherein can use by the multilayer material that squeezes the same polymer that press produces more.People's such as Kieffer US 4,789,699 in the revealed following patent of some other composite elastic material, the US 4,781 of Taylor, 966, US 4,657,802 and the US 4,652 of Morman, 487 and people's such as Morman US 4,655,760 and US 4,692,371.A kind of composite elastic material also can be a kind of like this form, but wherein collapsible fiber web is a kind of by the material of the constriction of constriction, is connected to then on the elastic sheet material, as is disclosed in the US5 of Morman, 226,992, US 4,981,747, and US 4,965,122 and US 5,336,545 in.

Term " clothes " means the non-medical relevant clothes of wearing of any kind as used herein.It comprises industrial work clothes, the Work Clothes that clothing link to each other, underwear, trousers, shirt, jacket, gloves, socks or the like.

Term " infect control goods " means medical relevant product as used herein, long gown and the cord used of surgery for example, mask, head covers image bouffant cap, and cap that surgery is used and guard shield, footgear resemble the footwear covering, boots cover and slippers, bandage, sterilization packaging thing, wipe the examination thing, clothes resemble the laboratory overcoat, Work Clothes, apron and jacket, patient's bedding, stretcher and cradle sheet material or the like.

Term " personal care product " means diaper as used herein, sport pants, absorbent undergarment, goods and the feminine hygiene article of having no control over oneself of being grown up.

" protective cover " means and is used for the vehicles such as automobile, truck, ship term as used herein; aircraft, motorcycle, bicycle; the covering of Caddy etc.; be used for usually being placed on the covering of the outer device of layer, described device such as grid, place and park equipment (hay mover; rotary tiller etc.); with the lawn facility, and floor covering, tablecloth and picnic mulching material.Test method

Melt flow rate (MFR): melt flow rate (MFR) (MFR) is the numerical value of polymer viscosity.MFR can be expressed as according to measure circulation timei under specific loads or shearing in the weight of known dimensions material capillaceous, and for example according to ASTM test 1238-90b with gram number/10 of set point of temperature and load measure minute.

Cyclic test: cyclic test is to use one can be finished by the Sintech 2 computer material testing systems that Sintech Incorporated ofStoughton.MA obtains.

For in the prolongation that stops to test or stretching, one 3 inches * 6 inches (sample (the long machine direction that is of a size of) of 76mm * 152mm) is placed in the jaw of Sintech 2 machines, and the gap between the jaw is 50mm.Sample is by the crosshead speed tractive of the stop load of one 2000 gram with 500mm/min then.With respect to the rate elongation with the percentage form at 2000 gram unstretched lengths is to be stretched to the amount of tension that stops to be worth.

Also obtained prolongation value to stop rate elongation under the experimental condition with intercept form.Intercept prolongation value is the percent stretch of turning point in load and the ratio of percent stretch figure.Numerical value is that 75% intercept rate elongation is used for the largest percentage that working sample is stretched in cyclic test.

In cyclic test, a kind of material is considered to fixing with respect to 75% intercept rate elongation and prolongs 5 times, and makes its original size of getting back to it, if can carry out like this.The measurement result that obtains is elongation load, hysteresis loss and answer load.This just can be used to design a kind of presentation graphs of final result, and for example at Fig. 1, in 2 and 3, the y axle is load, and the x axle is a rate elongation.This figure produces a curve, and it has a zone, is called " total energy absorption " or " TEA " under it.For the value that TEA curve ratio is and material, basic weight and sample width are irrelevant of the various circulations of a sample, it can compare with its sample.The accompanying drawing summary

Fig. 1 has represented the TEA curve of the composite elastic laminated product of control.Fig. 2 has represented the TEA curve of the composite elastic laminated product of example 1.Fig. 3 has represented the TEA curve of the composite elastic laminated product of example 2.Y-axis represents with the gram to be the load of unit, the rate elongation of X-axis in percentage being.Fig. 4 has represented to be suitable for the schematic diagram of the method for manufacturing technology that one of composite elastic material production is arranged in parallel.Detailed Description Of The Invention

Thermoplastic polymer is very useful in film, fiber and fibroreticulate product, and described product infects the control goods, the usefulness of various products such as clothes and protective covering for for example personal care articles.In some applications, it is desirable to, film, fiber and fiber web are flexible, so that by film, the product that fiber and fiber web are made can be fit to object, or do not have so that can carry out stretching a little and to be damaged.

Elastomeric polymer has been used among these application in the past, but its elastomeric polymer is some difficulty for technology.In the US 4,663,220 of Wisneski, disclosed a kind of method of improving the elastomeric polymer characteristic by interpolation a kind of polyolefin, especially polyethylene treating agent.In addition, these products have the special range of a stretching and shrinkage characteristic.

The applicant has produced a kind of laminated product that one deck is at least made by the novel species base polymer that has, and it had different stretchings and shrinkage characteristic before using.This laminated product has some useful especially characteristics, and its structure causes the user to allow the characteristic of film, fiber and fiber web layer stampings satisfy its accurate requirement in addition.

The polymer of new kind is relevant " metallocene " polymer or this polymer produced according to the metallocene technology.The metallocene technology is used a kind of metalloscene catalyst usually, and it is to be activated by a kind of cocatalyst, promptly is ionized.

Metalloscene catalyst comprises two (n-butyl cyclopentadienyl) titanium chloride, two (n-butyl cyclopentadienyl) zirconium dichloride, two (cyclopentadienyl group) scandium chloride, two (indenyl) zirconium chloride, two (methyl cyclopentadienyl) titanium chloride, two (methyl cyclopentadienyl) zirconium dichloride, cobaltocene, cyclopentadienyl group titanium trichloride, ferrocene, the dichloride hafnocene, isopropyl (cyclopentadienyl group ,-1-fluorenyl) zirconium dichloride, dichloride two luxuriant molybdenums, dicyclopentadienyl nickel, dichloride two luxuriant niobiums, ruthenocene, titanocene dichloride, the hydrochlorinate zirconocene, chlorination zirconocene or the like.One more detailed table of these compounds is included in people such as Rosen and transfers among the US 5,374,696 of Dow chemical company.These compounds also are disclosed in people such as Stevens and transfer among the US 5,064,802 of Dow.

Metallocene technology and catalyst and catalyst basic system that some are special are the themes of some patents.People's such as Kaminsky US 4,542,199 have described a kind of method, wherein cocatalyst weevil base aikyiaiurnirsoxan beta (MAO) joins in the toluene, adding general formula is the metallocene of (cyclopentadienyl group) 2MeRHal, and wherein Me is a transition metal, and Hal is a halogen, R is dipentadiene base or C1 to C6 alkyl, adds ethene then to form polyethylene.LaPointe etc. the people's and the USP 5,189,192 that transfers Dow chemical company a kind of process for preparing addition polymerization catalyst by the metal center oxidation has been described.Exxon Chemical Patents, the US 5,352,749 of Inc described a kind of in fluid bed the method for polymerization single polymerization monomer.US 5,349, and 100 have described the chiral metal cyclopentadinyl compound and selected hydride to shift the preparation method who produces chiral centre by mapping.

Cocatalyst is some materials as methylaluminoxane (MAO), and methylaluminoxane is the most general, also has alkyl aluminum in addition, the compound of boracic, and as three (pentafluorophenyl group) boron, four (pentafluorophenyl group) boron lithium and dimethylaniline four (pentafluorophenyl group) boron.Owing to handle and the contamination of products problem, therefore to other cocatalyst system or to greatest extent minimizing or even the possibility of saving alkyl aluminum constantly study.It is emphasized that metalloscene catalyst be activated or be ionized into the cation form be used for with the monomer reaction that is aggregated.

Use metalloscene catalyst to produce polymer and have the fabulous advantage that can make very narrow molecular weight ranges.Fig. 1 has represented that its metalloscene catalyst has provided narrower curve for a Ziegler-Natta catalyst and a metallocene-type catalyst typical molecular weight distribution situation relatively.It is possible for the metallocene-produced polymer that polydispersity quantity (Mw/Mn) is lower than 4 even low 2.When comparing with other polymer that is similar to Ziegler-Natta catalyst production, the chain branching that these polymer have narrow weak point distributes.

When using the stereotaxis metalloscene catalyst, then might utilize metallocene catalyst systems to come the very approaching isotacticity of controlling polymers.In fact, the polymer of having produced has the isotacticity above 99%.Also possible is to utilize this system, can produce high syndiotactic polypropylene.

The isotacticity of controlling polymers can also the result form such polymeric articles, and it contains the block of isotactic block and the atactic material of alternation on the whole length of polymer chain.This structure partly produces a kind of elastomeric polymer according to atactic.This polymer synthetic by K.B.Wagne in magazine " science ", discuss in 267 volume (1995.1.13) articles P.191.In the achievement that Coates and Waymouth are discussed, Wanger explains that catalyst vibrates between three-dimensional chemical configuration, produce a kind of polymer chain with development length of the isotaxy stereocenter on the development length that is connected to the atactic center.Thereby the isotaxy domination reduces generation elasticity.Geoffrey W.Coates has delivered one piece of autograph with Roberr M.Waymouth the 217th page of identical publication and has been " the upright structure rule of vibration positive control: for the synthetic strategy of thermoplastic elastic polypropylene ", this article has been discussed their work, wherein they are under the situation that methylaluminoxane (MAO) arranged, two (2-benzene indenyl) zirconium dichlorides have been used, and in reactor, change pressure and temperature, the polymer form of vibration between isotaxy and atactic.

The commercial prod of metallocene polymers is subjected to certain limitation.But the development.These polymer can be by Exxon Chemical company of Baytown, and Texas obtains under based on the EXXPOL  of polyacrylic polymer and ACHIEVETM and the trade name based on the EXACT  of polyacrylic polymer and EXCEEDTM.Dow Chemical Company of Midland, Michigan have the commercial polymer that obtains under ENGAGE  by name.These materials are considered to utilize non-stereotaxis metalloscene catalyst to produce.Exxon it has been generally acknowledged that their metalloscene catalyst technology is " (single site) puts in unit " catalyst, and Dow thinks " constrained geometry " under INSITE  by name, to be different from traditional Ziegler-Natta catalyst with many response locations.Some other producer is Fina Oil for example, BASF, and Amoco, Hoechst and Mobil also are very positive in this field, and believe the following 10 years utilization rates according to the polymer of this technology production and will increase.Especially in situation of the present invention, elastic polyolefin such as polypropylene and polyethylene are well-adapted.

Relevant elastomeric polymer based on metallocene, people's such as Kaminsky US 5,204,429 has described a kind of process, it can use a kind of catalyst to produce elastocopolymer by cyclenes and linear alkene, and its catalyst is luxuriant transistion metal compound of solid rigid chiral metal and aikyiaiurnirsoxan beta.Polymerisation be a kind of atent solvent such as aliphatic series or cycloaliphatic hydrocarbon for example finish in the toluene.Use is treated the monomer of polymerization as solvent, and reaction also gas phase can occur.People's such as Lai US that transfers DowChemical 5,278,272 and US 5,272,236 and " significantly flexible linear olefine polymer " by name have been described polymer and have been had special elastic characteristic.Elastic polyolefin under the also large quantities of a series of trade names of production " ENGAGE "  of Dow.

Being used for some other elastomeric thermoplastic polymers of the present invention can be made by certain block copolymers, polyurethanes for example, copolyether ester, polyamide polyether block copolymer, ethylene vinyl acetate (EVA), having common structural formula is A-B-A ', A-B-A-B, or the block copolymer of A-B, resemble copolymerization (styrene/ethylene-butylene), (polystyrene/poly-(ethene-butylene)/polystyrene), poly-(styrene/ethylene-butylene/styrene), or the like.

Useful elastic resin comprises that having general structure is A-B-A ', or the block copolymer of A-B, and A and A ' respectively are a kind of thermoplastic polymer end-blocks, it contains a cinnamic part, for example poly-(ethene aromatic hydrocarbons), and B is a kind of middle block of elastomeric polymer, for example conjugated diene or low olefin polymerization thing.A-B-A ' type block copolymer can have different or identical thermoplastic block polymer to A with A ' block, and this block copolymer mean comprise linear, branching and radial block copolymer.About this point, radial block copolymer can be expressed as (A-B) _m-X, wherein X is atom or the molecule that many palaces can be rolled into a ball, and each (A-B) _m-be to be that end-blocked mode spreads with A by X.In radial block copolymer, X can be that atom or molecule can be rolled into a ball in many palaces of organic or inorganic, and m is the integer with script functional group that is present in X of identical value, and it is 3 usually at least, generally is 4 or 5, but is not limited to these.Like this, in the present invention, described " block copolymer ", especially " A-B-A ' " and " A-B " block copolymer means and comprises having as above-mentioned like the block of rubber and all block copolymers of thermoplastic block, they can be extruded (as being melted and sprayed spinning), and do not limit block quantity.For example, lofty nonwoven fibre web can be made of elasticity (polystyrene/poly-(ethene-butylene)/polystyrene) block copolymer.The commercialized example of these elastocopolymers is for example to be called KRATON  material, and they can be by Shell ChemicalCompany of Houston, and Texas obtains.KRATON  block copolymer can obtain some different prescriptions, and their quantity determines at US 4,663, in 220, draws at this and to be reference.

The polymer of being made up of elasticity A-B-A '-B ' Tetrablock copolymer also can be particularly useful among the present invention, and such polymer is described among people's such as Taylor the US 5,332,613.In such polymer, A is a thermoplastic polymer block, and B is the isoprene monomeric unit that actual and poly-(ethylene-propylene) monomeric unit hydrogenation is closed.An example of such Tetrablock copolymer is styrene-poly-(ethylene-propylene)-styrene-poly-(ethylene-propylene) or SEPSEP elastic block copolymer, can be by Shell Chemical Company of Houston, Texas, trade name KRATON  G-1657 obtains down.

The thermoplastic copolyester elastomer comprises the copolyether ester with following general structural formula

Wherein " G " is selected from the following combination that constitutes: poly-(oxygen ethene)-α, and omega-diol, poly-(oxypropylene)-α, omega-diol, poly-(tetramethylene)-α, omega-diol, and " a ", " m " and " n " is positive integer.These materials have about 600%～750% elongation at break usually when measuring according to ASTM D-638, have the fusing point of about 350～400 (176-205 ℃) when bill ASTM D-2117 measures.

The commercialized example of such copolyester material for example is called ARNITEL , in the past can be from Akzo Plastics of Arnhem, Holland obtains DSM of Sittard, Holland obtains, or be called HYTREL , they can be from E.I.DuPont de Nemours ofWilmington, and Delaware obtains.The lofty nonwoven fibre web that is formed by the polyester elastomeric material for example is disclosed in, among people's such as Morman the US 4,741,949, but in this incorporated by reference.

The elastomeric material of other example that can be used comprises for example urethane elastomer, and they can be from B.F.Goodrich ﹠amp under trade mark ESTANE ; Co. or MORTHANE  obtain from Morton Thiokol Corp., the polyamide polyether block copolymer, for example be called PEBAX , can be from Atochem Inc.Polymers Division (RILSAN ), of GlenRock, New Jersey obtains and the polyester elastomeric material, for example can be from E.I.DuPont De Nemours ﹠amp under trade name HYTREL ; Company obtains.

Elastomeric polymer also comprises the copolymer of ethene and at least one vinyl monomer, and its vinyl monomer is vinylacetate for example, the ester class of undersaturated mono carboxylic acid of aliphatic series and such monocarboxylic acid.These elastocopolymers and for example be disclosed in US4 by the lofty nonwoven fibre web that its elastocopolymer forms are in 803,117.

Also possible is that other material that mixes with elastomer is used for producing according to layer material of the present invention, for example the fluorocarbon chemical products is to strengthen chemoresistance, these are all taught at US5,178, in 931, for example be used to increase anti-fire retardant and/or the colorant that fires and make each layer have identical or different color.Being used for fire retardant and colorant spunbond and that melt and spray thermoplastic polymer is known technology and is internal additives.If you are using, the common consumption of colorant is less than 5% of layer material weight, and other buildup of material amount is less than 25% (weight).

Product by laminated product manufacturing of the present invention also can be subjected to relevant processing, makes it be suitable for more dedicated functions.These are known technologies about the method for handling and it is suitable for, and comprise for example anti-Ethanol Treatment, antistatic treatment and similar processing, and it is by spraying, and the impregnating mode is implemented.Using Zelec  antistatic additive (can be from E.I.DuPont, Wilmington, Delaware acquisition) is this relevant example handling.

When laminated product of the present invention was form with nonwoven web, they can melt and spray or spunbond technology is produced by known in the art.These technologies use an extruder the thermoplastic polymer of fusion is provided to a spinning plate place usually, are produced fiber thereby locate polymer at this by fibration, and this fiber can be weak point or long.These fibers are stretched by air subsequently usually, and are placed on a mobile formed mat or are with the formation nonwoven web.With these fibers spunbond and that the melt-blown process technology is produced is some microfibers as defined above.

Spunbond bondedfibre fabric is usually in some way by in advance or at first bonding, is in order to give their enough structural intergrities, so that withstand the severe further processing to finished product as their production.This pre-bonding can finishing by pressure roller or by the hot-air scraper, aid adhesion can realize as follows that waterpower is twined, acupuncture, ultrasonic wave is bonding, and adhesive is bonding, and loop bonding is bonding, bonding and hot melt adhesive in the air.

The multilayer meltblown fabric can pass through needle point method, ultrasonic wave Method for bonding, adhesive connection method, hot melt method and extrusion coated method and bonded.

An embodiment of multi-layer laminate is a kind of embodiment, and wherein some layer is spunbond, and some melts and sprays, for example a kind of spunbond/meltblown/spunbonded (SMS) laminated product is disclosed in people's such as Brock US 4,041,203, people's such as Collier US 5,169,706 and the US 4,374 of Bornslaeger, in 888, its whole contents can be drawn at this and is reference.This laminated product is by at first the nonwoven fabric layer being placed on the formed strip that moves in order, place a meltblown fabric layer then and reach another spunbond layer at least, and bonding in the above described manner subsequently this laminated product being made.In addition, tissue layer can be made respectively, they is collected on some rollers, and in an independent adhesion step and combine, and this content illustration is at US 4,720, in 415, can draw at this its full content and to be reference.The basic weight that such multi-layer laminate has usually is 0.1～12osy (6 to 400gsm), especially 0.75～3osy.

Composite elastic material of the present invention has the elastomeric polymer layer and a contractile fiber web of at least one elastic polyolefin layer and at least one other type.It is online that this fiber web is connected to elastomer.This is attainable, when elastic webs is stretched and/or and collapsible fiber web by constriction.Elastic polyolefin is preferably made by the metallocene process.Might be two collapsible fiber webs; One this fiber web is arranged on every side of elastic layer, also might be the multilayer elastic layer.The elastic layer material can be arranged with following manner, and for example, the elastic polyolefin material has the polymer elasticity layer of other type in the centre on each side of elastic polyolefin material, and last collapsible being adhered on each other elastic layer.Laminated product can have elastic polyolefin layer in the centre, other elastic layer on every side, the added resilience polyolefin layer on the every side of other elastic layer and last shrinkable layers be as skin then.The quantity of layer and arrangement only are subjected to the restriction of equipment and imagination.

Collapsible fiber web of the present invention can be a polyolefin, and for example polyacrylic spun-bonded fibre net maybe can be other appropriate materials, the elastic characteristic that it is not defined as above.

Fig. 4 has represented a kind of continuous manufacturing one row formula process schematic diagram that is used for stretched bonded elasticity and collapsible fiber web are made laminated product, but wherein two collapsible fiber webs are positioned on each opposite side of a drawing of fiber net that is made of two elastomeric polymers.In the drawings, elastomeric polymer is placed on the shaped wire 2 by respectively melting and spraying device for spinning 1, and makes an elastic webs 3, and shaped wire 2 is placed speed with certain first speed such as layer material and moved.Elastic webs 3 moves forward and by bond roll 6,7, in this case, elastic webs 3 combines with two collapsible fiber webs 4,5 of unwinding from the storage roller herein.Shown bond roll the 6, the 7th is made up of a calender 6 and the smooth anvil roller 7 by pattern, but aforesaid other method and apparatus also can use at this.Fiber web 3,4,5 with the direction operation shown in the arrow relevant with each storage roller with the roller of shaped wire 2.Elastic webs 3 is to be stretched to desirable quantitative value by following manner, and promptly bond roll 6,7 rotates with the speed greater than shaped wire 2, produces the velocity ratio of a bond roll/shaped wire.Pressure between the roller 6,7 is adhered to collapsible fiber web 4,5 on the elastic webs 3, thereby forms a kind of composite elastic material 8.Composite elastic material 8 is winding on the winch spool 9 subsequently.

What the inventor obtained is a kind of like this laminated product, promptly wherein at least one deck preferably make less than 4 elastic polyolefin by polydispersity, at least other elastomeric polymer layer of one deck, also has the non-resilient collapsible fiber web of one deck, make some elastic characteristics of the product made by this laminated product, as hysteresis quality, can be accurately controlled.Especially the laminated product that has poly-(styrene/ethylene-butylene/styrene) block copolymer layer of an elastic polyolefin layer and an elasticity and the collapsible polypropylene fiber net on each side, being formed with very, good mixing stretches and the retraction feature.

For the advantage of the laminated product according to the present invention is described, provide following examples and Comparative Examples.Note that the process conditions that are used for producing these laminated products are given at table 1.

Comparative Examples

Use melts and sprays internal layer as an elasticity of the polypropylene spun-bonded skin of collapsible fibroreticulate 0.4osy (13.6gsm) and Shell ' s Kraton  G-2755 poly-(styrene/ethylene-butylene/styrene) or SEBS resin, makes two samples of composite elastic material.When elasticity meltblown layer usefulness bonding/line that it is as shown in the table compares stretching, outer by hot melt adhesive, to produce laminated product with 13% adhesion area pattern.

Example 1

Use as the polypropylene spun-bonded skin of collapsible fibroreticulate 0.4osy (13.6gsm) and have under 190 ℃ and 2160gm load melt-flow index and melt and spray 3 samples that internal layer is made composite elastic material as one of Dow ' s ENGAGE  58200.02 metallocene polymers of 30g/m.When elasticity meltblown layer usefulness bonding/line as shown in Table compared stretching, outer hot melt adhesive was to produce the laminated product with 13% adhesion area case figure decorative pattern.

Example 2

Two samples of composite elastic material are made in use as one second internal layer that melts and sprays internal layer and Dow ' s ENGAE  58200.02 polymer of polypropylene spun-bonded skin of collapsible fibroreticulate 0.4osy (13.6gsm) and Shell ' s Kraton  G-2755 polymer.When elasticity melted and sprayed internal layer employing bonding/line as shown in Table than stretching, outer hot melt adhesive was to produce the laminated product with 13% adhesion area case figure decorative pattern.

Comparative Examples and example are tested tensile properties according to above-mentioned loop test mode down in " test method ", and its result is published in the table 1.In table, abbreviation EXT refers to " stretching ", and RET refers to " retraction ", and STS refers to " stopping to stretch ", and MB refers to " melting and spraying ", and BW refers to " basic weight ".

	Laminated product basic weight GSM	Be pulled to the percentage elongation % when stopping	1 EXT TEA circulates	1 RET TEA circulates	5 EXT TEA circulate	Circulation 5/1 EXT/TEA ratio	The place's load of damming, g	Circulation percentage elongation %	The load of 30% percentage elongation, g	The load of 40% o'clock percentage elongation, g	Load during the circulation elongation, g	Melt temperature, F	The air degree, F	Bonding/the line ratio	Tack temperature, F (set)
																Example 2	64	86.9	30.5	20.4	21.7	0.7115	854	60	420	515	680	455	491	2.9	135
Example 2	56	111.3	44.5	28.1	30.8	0.6921	927	80	368	461	735	455	491	3.8	135
																Example 1	65	83.3	30.9	20.2	20.3	0.6570	871	60	415	527	730	466	477	4.2	145
Example 1	70	74.2	27.2	16.4	16.7	0.6139	813	60	356	462	681	431	438	2.8	170
																Example 1	65	90	28.9	17.6	17.9	0.6194	774	60	378	497	725	401	438	4.2	170
Comparative Examples	47	151.4	30.7	20	21.2	0.6906	957	60	436	513	618	-500	474	3.2	130
																Comparative Examples	47	151.4	49.9	29.3	31.8	0.6373	957	80	460	535	716	-500	474	4.5	130

This table is expressed in laminated product, by the layer material of elastic polyolefin and non-polyolefin elastomer is provided, good stretching control and retraction characteristic are possible, and might make a kind of laminated product that has more or less stretching and better or poorer retraction than other laminated product.This control makes the user of the product of being made by laminated product of the present invention can allow its product satisfy service object's needs more accurately, because product will provide desired stretching, and also desired just, this also can make expense reduce.For example, produce a kind of laminated product, the laminated product that provides a kind of ratio to have an elastic polyolefin layer and the elasticity SEBS on its each side is had the laminated product of different stretch and retraction feature with an elastic polyolefin layer and the elastomeric polyurethane layer on its each side.The elastic polyolefin layer is placed on will be provided on each side of flexible polyether ester and above-mentioned two kinds of laminated products with different hysteresis.

Although minority embodiment of the present invention describes in detail in the above, those skilled in the art will be readily appreciated that some improvement may be accomplished according to these embodiment, and can not break away from novel teachings of the present invention and advantage in fact.Therefore, all improve and all plan to comprise in the present invention and the claim scope subsequently.

In the claims, method adds that it is the structure of finishing recited function that what is claimed is of function is used for covering described herein, not only comprises structural equivalent, and comprises equivalent configurations.Therefore, although nail and screw may structure not be equal to, because nail uses a cylindrical surface and wooden part to be fixed together, and screw uses a helicoid and wooden part to be fixed together, and divides in the occasion at fastening xylem, and nail can be equivalent structure with screw.

Claims (17)

1. controlled hysteresis composite elastic material comprise the ground floor of the luxuriant polyolefin layer of one deck elastic metallic, and it connects the other layer of one deck at least, this other layer is to be made of elastomeric polymer, it is selected from the kind that comprises what follows: polyurethanes, copolyether ester, polyamide polyether block copolymer, ethylene vinyl acetate (EVA), with general formula be A-B-A ', A-B-A-B, or the block copolymer of A-B, above-mentioned layer also connects one the 3rd layer, and this layer is a kind of collapsible fiber web.

2. according to the material of claim 1, wherein said polyolefin has and is less than 4 polydispersity.

3. according to the material of claim 1, wherein said the 3rd layer is neck stretched when connecting.

4. according to the material of claim 1, the other layer of wherein said ground floor and described one deck is stretched when being connected in described collapsible fiber web.

5. according to the material of claim 1, wherein said layer is to comprise that by being selected from what follows the method for kind is joined together: needle point method, adhesive is bonding, hot melt adhesive, and extrusion coated.

6. according to the material of claim 1, the other layer of wherein said ground floor and described one deck is a film.

7. according to the material of claim 1, the other layer of wherein said one deck at least is a kind of fiber web that is made of fiber, this fiber is to be selected from the polymer that comprises following kind, polyurethanes, copolyether ester, polyamide polyether block copolymer, ethylene vinyl acetate (EVA), copolymerization (styrene/ethylene-butylene), (polystyrene/poly-(ethene-butylene)/polystyrene) and poly-(styrene/ethylene-butylene/styrene).

8. according to the material of claim 1, wherein said ground floor is a kind ofly to be less than the meltblown fiber web of 4 the microfibre that elastic polyolefin constituted by having degree of polymerization dispersiveness, and described one deck at least in addition is the meltblown fiber web that is made of poly-(styrene/ethylene-butylene/styrene).

9. personal care product is selected from and comprises following kind: diaper, and sport pants, absorbent undergarment, adult's product of having no control over oneself, and feminine hygiene article, this personal care product is made of the described meltblown fibers net materials of claim 8.

10. according to the personal care product of claim 9, it is a kind of diaper.

11. according to the personal care product of claim 9, it is a kind of absorbent undergarment.

12. according to the personal care product of claim 9, it is a kind of adult product of having no control over oneself.

13. according to the personal care product of claim 9, it is a kind of feminine hygiene article.

14. controlled hysteresis composite elastic material, it comprises the ground floor of the metallocene polyolefin layer that is made of less than 10 microns fiber average diameter, and it connects the second layer of one deck average diameter less than 10 microns fiber formation, it is by being selected from the elastomeric polymer that comprises following kind, polyurethanes, copolyether ester, the polyamide polyether block copolymer, ethylene vinyl acetate (EVA), with general formula be A-B-A ', A-B-A-B, or the block copolymer of A-B, above-mentionedly two-layerly also connect one the 3rd layer, this layer is the collapsible fiber web that is made of greater than 7 microns fiber average diameter.

15. according to the material of claim 14, wherein said ground floor is stretched when being connected its 3rd layer with the second layer.

16. according to the material of claim 14, wherein it also comprises another collapsible fiber web that the average diameter that is connected to ground floor constitutes greater than 7 microns fiber.

17. material according to claim 14, it also comprises the 4th layer that is made of less than 10 micrometer fibers average diameter, its fiber constitutes by being selected from the elastomeric polymer that comprises following kind: polyurethanes, copolyether ester, the polyamide polyether block copolymer, ethylene vinyl acetate (EVA), with general formula be A-B-A ', A-B-A-B, or the block copolymer of A-B, it connects ground floor, and has average diameter and be connected on described the 4th layer greater than the contractile layer 5 that 7 microns fiber constitutes, wherein the first, the second when being connected, be stretched with the 4th layer.

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